本研究分為兩部份，分別為網印式電解質的開發與奈米碳管(CNT)作為電解質處理劑於染料敏化太陽能電池(DSSC)之應用。在網印式電解質的製備上，首先使用聚乙二醇(PEO)作為增稠劑，藉由PEO濃度的控制以達到良好的塗佈行為。接著，利用氧化鋅(ZnO)與二氧化鈦(TiO2)奈米粒子作為電解質添加劑，探討此兩種奈米粒子對元件特性的影響。實驗結果顯示ZnO的使用會影響導帶能階位置，產生更大的元件開路電壓，而TiO2則可降低電荷在對電極/電解質界面上的轉移阻力。最後基於網印製程的使用，本研究將含有ZnO與TiO2奈米粒子添加的電解質分別印製於光電極與對電極上，組裝成具雙層電解質結構的DSSC元件，希望能取得此二種奈米粒子的優點。相較於未使用奈米粒子之元件，此雙層結構可使DSSC之開路電壓由0.744 V提升至0.808 V，同時光電轉換效率可由8.19%提高至8.53%。
在第二部份，CNT是作為電解質之添加劑或處理劑。因CNT添加於一般膠態電解質時，有分散不易的問題，所以本研究中將CNT作為液態電解質處理劑。實驗結果發現，液態電解質經5 wt.% CNT處理之後，可使DSSC之開路電壓由0.753 V升高至0.792 V，而光電轉換效率則由8.26%提升至9.18%。進一步以紫外光-可見光吸收光譜與拉曼光譜分析後可得知，電解質經過CNT處理之後，三碘及多碘陰離子之含量會有所降低，因此位於光電極/電解質界面的電荷再結合反應較不易發生，進而改善元件的效能。

There are two different topics in this study. The first is estabilishment of screen-printing electrolyte, and the second is applying carbon nanotube (CNT) as the additive agent and treating agent of electrolyte.
For the estabilishment of screen-printing electrolyte, PEO was added into electrolyte to prepare printable electrolyte and controlled the amount of PEO to adjust viscosity of electrolyte. Then two kinds of nano-fillers were induced. ZnO in the electrolyte would make the counduction of photo electrode shift negatively to increase Voc. TiO2 in the electrolyte would decrease resistance bwtween counter electrode and electrolyte to increase Jsc. Due to screen printing process of electrolyte, make electrolyte containing ZnO and TiO2 printed on photo electrolyte and counter electrode respectively to prepare DSSC with double layer electrolyte. By combining both of their advantages, double layer electrolyte could enhance Voc up to 0.808V leading to a higher efficiency of 8.53%.
In the second topic, CNT was used as additive agent and treating agnet of electrolyte.
To solve the problem of poor dispersion in printable electrolyte, CNT applied as treating agnet for liquid-state electrolyte. Utilizing electrolyte which was treated by 5 wt%. CNT could induce higher voltage of 0.792V and higher efficiency of 9.18%. In UV-vis and Raman analysis, it shows that concentration of triiodine and polyiodine would decrease by the treatment of CNT. it would make the resistance between photo electrode and electrolyte to enhance the performance of DSSC.

[1] H. Tsubomura, M. Matsumura, Y. Nomura, and T. Amamiya, "Dye sensitized zinc oxide: aqueous electrolyte: platinum photocell," Nature, 261, 402-403 (1976).
[2] B. O’Regan and M. Grätzel, "A low-cost, high-efficiency solar cell based on dye-sensitized colloidal TiO2 films," Nature, 353, 737-739 (1991).
[3] A. Pandikumar, S.-P. Lim, S. Jayabal, N. M. Huang, H. N. Lim, and R. Ramaraj, "Titania@gold plasmonic nanoarchitectures: An ideal photoanode for dye-sensitized solar cells," Renew. Sust. Energ. Rev., 60, 408-420 (2016).
[4] M. Grätzel, "Conversion of sunlight to electric power by nanocrystalline dye-sensitized solar cells," J. Photochem. Photobiol. A-Chem., 164(1-3), 3-14 (2004).
[5] M. Grätzel, "Solar energy conversion by dye-sensitized photovoltaic cells," Inorg. Chem., 44, 6841-6851 (2005).
[6] A. Hagfeldt, G. Boschloo, L. Sun, L. Kloo, and H. Pettersson, "Dye-sensitized solar cells," Chem. Rev., 110, 6595-6663 (2010).
[7] Y.-Y. Kuo and C.-H. Chien, "Sinter-free transferring of anodized TiO2 nanotube-array onto a flexible and transparent sheet for dye-sensitized solar cells," Electrochim. Acta, 91, 337-343 (2013).
[8] H. C. Weerasinghe, P. M. Sirimanne, G. V. Franks, G. P. Simon, and Y. B. Cheng, "Low temperature chemically sintered nano-crystalline TiO2 electrodes for flexible dye-sensitized solar cells," J. Photochem. Photobiol. A-Chem., 213(1), 30-36 (2010).
[9] S. Ito, N. C. Ha, G. Rothenberger., P. Liska, P. Comte, S. M. Zakeeruddin, P. Péchy, M. K. Nazeeruddin, and M. Grätzel, "High-efficiency (7.2%) flexible dye-sensitized solar cells with Ti-metal substrate for nanocrystalline-TiO2 photoanode," Chem. Commun., 38, 4004-4006 (2006).
[10] M. Grätzel, "Photoelectrochemical cells.," Nature, 414, 338-344, (2001).
[11] X. Feng, K. Shankar, O. K. Varghese, M. Paulose, T. J. Latempa, and C. A. Grimes, "Vertically aligned single crystal TiO2 nanowire arrays grown directly on transparent conducting oxide coated glass: synthesis details and applications," Nano Lett., 8, 3781-3786 (2008).
[12] J. Jiu, S. Isoda, F. Wang, and M. Adachi, "Dye-sensitized solar cells based on a single-crystalline TiO2 nanorod film," J. Phys. Chem. B, 110, 2087-2092 (2006).
[14] A. Hagfeldt and M. Grätzel, "Molecular photovoltaics," Acc. Chem. Res., 33(5), 269-277 (2000).
[15] M. K. Nazeeruddin, A. Kay, I. Rodicio, R. Humphry-Baker, E. Muller, P. Liska, N. Vlachopoulos, and M. Grätzel, "Conversion of light to electricity by cis-X2Bis(2,2’-bipyridyl-4,4’-dicarboxylate)ruthenium(II) charge-transfer sensitizers (X = Cl-, Br-, I-, CN-, and SCN-) on nanocrystalline TiO2 electrodes," J. Am. Chem. Soc., 115, 6382-6390, (1993).
[16] M. K. Nazeeruddin, P. Péchy, and M. Grätzel, "Efficient Panchromatic Sensitization of Nanocrystalline TiO2 films by a black dye based on a trithiocyanato–ruthenium complex," Chem Commun., 18, 1705-1706 (1997).
[17] M. K. Nazeeruddin, F. D. Angelis, S. Fantacci, A. Selloni, G. Viscardi, P. Liska, S. Ito, B. Takeru, and M. Grätzel, "Combined experimental and DFT-TDDFT computational study of photoelectrochemical cell ruthenium sensitizers," J. Am. Chem. Soc., 127, 16835-16847 (2005).
[18] P. Wang, C. Klein, R. Humphry-Baker, S. M. Zakeeruddin, and M. Grätzel, "A high molar extinction coefficient sensitizer for stable dye-Sensitized solar cells," J. Am. Chem. Soc., 127, 808-809 (2004).
[19] C. Y. Chen, M. Wang, J. Y. Li, N. Pootrakulchote, L. Alibabaei, C. Ngoc-le, J.Decoppet, J. H. Tsai, C. Grätzel, C. G. Wu, S. M. Zakeeruddin, and M. Grätzel, "Highly efficient light-harvesting ruthenium sensitizer for thin-film dye-sensitized solar cells," ACS nano, 3, 3103-3109 (2009).
[20] Q. Yu, Y. Wang, Z. Yi, N. Zu, J. Zhang, M. Zhang, and P. Wang, "High-efficiency dye-sensitized solar cells: the influence of lithium ions on exciton dissociation, charge recombination, and surface states," ACS nano, 4, 6032-6038 (2010).
[21] T. Bessho, S. M. Zakeeruddin, C. Y. Yeh, W. G. Diau, and M. Grätzel, "Highly efficient mesoscopic dye-sensitized solar cells based on donor-acceptor-substituted porphyrins," Angew. Chem. Int. Ed., 49, 6646-6649 (2010).
[22] A. Yella, H. W. Lee, H. N. Tsao, C. Yi, A. K. Chandiran, M. Nazeeruddin, W. G. Diau, C. Y. Yeh, S. M Zakeeruddin, M. Grätzel, "Porphyrin-sensitized solar cells with cobalt (II/III)–based redox electrolyte exceed 12 percent efficiency," science, 334(6056), 629-634 (2011).
[23] S. Mathew, A. Yella, P. Gao, R. Humphry-Baker, B. F. E. Curchod, N. Ashari-Astani, I. Tavernelli, U. Rothlisberger, M. Nazeeruddin, and M. Grätzel, "Dye-sensitized solar cells with 13% efficiency achieved through the molecular engineering of porphyrin sensitizers," Nature Chem., 6, 242-247 (2014).
[24] S. Ito, S. M. Zakeeruddin, R. Humphry‐Baker, P. Liska, R. Charvet, P. Comte, M. K. Nazeeruddin, P. Péchy, M. Takata, H. Miura, S. Uchida, and M. Grätzel, "High-efficiency organic-dye-sensitized solar cells controlled by nanocrystalline-TiO2 electrode Tthickness," Adv. Mater., 18, 1202-1205 (2006).
[25] S. Ito, H. Miura, S. Uchida, M. Takata, K. Sumioka, P. Liska, P. Comte, P. Péchyb, and M. Grätzelb, "High-conversion-efficiency organic dye-sensitized solar cells with a novel indoline dye," Chem Commun., 41, 5194-5196 (2008).
[26] G. Zhang, H. Bala, Y. Cheng, D. Shi, X. Lv, Q. Yu, and P. Wang*, "High efficiency and stable dye-sensitized solar cells with an organic chromophore featuring a binary pi-conjugated spacer," Chem Commun., 16, 2198-2200 (2009).
[27] W. Zeng, Y. Cao, Y. Bai, Y. Wang, Y. Shi, M. Zhang, F. Wang, C. Pan, and P. Wang, "Efficient Dye-sensitized solar cells with an organic photosensitizer featuring orderly conjugated ethylenedioxythiophene and dithienosilole blocks," Chem. Mater., 22, 1915-1925 (2010).
[28] K. Kakiage, Y. Aoyama, T. Yano, K. Oya, J. Fujisawa, and M. Hanaya, "Highly-efficient dye-sensitized solar cells with collaborative sensitization by silyl-anchor and carboxy-anchor dyes," Chem Commun., 51, 15894-15897 (2015).
[29] G. Wolfbauer, A. M. Bond, J. C. Eklund, and D. R. MacFarlane, "A channel flow cell system specifically designed to test the efficiency of redox shuttles in dye sensitized solar cells," Sol. Energy Mater. Sol. Cells, 70(1), 85-101 (2001).
[30] S. Nakade, T. Kanzaki, W. Kubo, T. Kitamura, Y. Wada, and S. Yanagida, "Role of electrolytes on charge recombination in dye-sensitized TiO2 solar cell (1): the case of solar cells using the I－/ I3－redox couple," J. Phys. Chem. B, 109, 3480-3487 (2005).
[31] R. Harikisun, and H. Desilvestro, "Long-term stability of dye solar cells," Solar Energy, 85, 1179-1188 (2011).
[32] P. Balraju, P. Suresh, M. Kumar, M. S. Roy, and G. D. Sharma, "Effect of counter electrode, thickness and sintering temperature of TiO2 electrode and TBP addition in electrolyte on photovoltaic performance of dye sensitized solar cell using pyronine G (PYR) dye," J. Photochem. Photobiol. A-Chem., 206, 53-63 (2009).
[33] T. Stergiopoulos, I. M. Arabatzis, G. Katsaros, and P. Falaras, "Binary polyethylene oxide/titania solid-state redox electrolyte for highly efficient nanocrystalline TiO2 photoelectrochemical cells," Nano lett., 2(11), 1259-1261 (2002).
[34] H. Greijer Agrell, J. Lindgren, and A. Hagfeldt, "Coordinative interactions in a dye-sensitized solar cell," J. Photochem. Photobiol. A-Chem., 164(1-3), 23-27 (2004).
[35] T. W. Hamann, "The end of iodide? Cobalt complex redox shuttles in DSSCs," Dalton Trans., 41(11), 3111-3115 (2012).
[36] S. M. Feldt, G. Wang, G. Boschloo, and A. Hagfeldt, "Effects of driving forces for recombination and regeneration on the photovoltaic performance of dye-sensitized solar cells using cobalt polypyridine redox couples," J. Phys. Chem. C, 115, 21500-21507 (2011).
[37] Y. L. Lee, C. L. Chen, L. W. Chong, C. H. Chen, Y. F. Liu, and C. F. Chi, "A platinum counter electrode with high electrochemical activity and high transparency for dye-sensitized solar cells," Electrochem. Commun., 12, 1662-1665 (2010).
[38] L. L. Li, C. W. Chang, H. H. Wu, J. W. Shiu, P. T. Wu, and W. E. Diau, "Morphological control of platinum nanostructures for highly efficient dye-sensitized solar cells," J. Mater. Chem., 22(13), 6267-6273 (2012).
[39] E. Olsen, G. Hagen, and S. E. Lindquist, "Dissolution of platinum in methoxy propionitrile containing LiI/I2," Sol. Energy Mater. Sol. Cells, 63, 267-273 (2000).
[40] T. N. Murakami, S. Ito, Q. Wang, M. Nazeeruddin, T. Bessho, I. Cesar, P. Liska, R. Humphry-Baker, P. Comte, P. Péchy, and M. Grätzelz, "Highly efficient dye-sensitized solar cells based on carbon black counter electrodes," J. Electrochem. Soc., 153(12), A2255-A2261 (2006).
[41] K. C. Huang, Y. C. Wang, R. X. Dong, W. C. Tsai, K. W. Tsai, C. C. Wang, Y. H. Chen, R. Vittal, J. J. Lin, and K. C. Ho, "A high performance dye-sensitized solar cell with a novel nanocomposite film of PtNP/MWCNT on the counter electrode," J. Mater. Chem., 20, 4067-4073, 2010.
[42] L. Kavan, J. H. Yum, and M. Grätzel, "Optically transparent cathode for dye-sensitized solar cells based on graphene nanoplatelets," Acs Nano, 5, 165-172, 2010.
[43] J. M. Pringle, V. Armel, and D. R. MacFarlane, "Electrodeposited PEDOT-on-plastic cathodes for dye-sensitized solar cells," Chem. Commun., 46, 5367-5369, 2010.
[44] F. Cao, G. Oskam, and P. C. Searson, "A solid state, dye sensitized photoelectrochemical cell," J. Phys. Chem., 99, 17071-17073 (1995).
[45] P. Wang, S. M. Zakeeruddin, I. Exnar, and M. Grätzel, "High efficiency dye-sensitized nanocrystalline solar cells based on ionic liquid polymer gel electrolyte," Chem. Commun., 24, 2972-2973 (2002).
[46] P. Wang, S. M. Zakeeruddin, J. E. Moser, M. K. Nazeeruddin, T. Sekiguchi, and M. Gratzel, "A stable quasi-solid-state dye-sensitized solar cell with an amphiphilic ruthenium sensitizer and polymer gel electrolyte," Nature Mater., 2(6), 402-407 (2003).
[47] C. L. Chen, H. Teng, and Y. L. Lee, "Preparation of highly efficient gel-state dye-sensitized solar cells using polymer gel electrolytes based on poly(acrylonitrile-co-vinyl acetate)," J. Mater. Chem., 21, 628-632 (2011).
[48] C. L. Chen, H. Teng, and Y. L. Lee, "In situ gelation of electrolytes for highly efficient gel-state dye-sensitized solar cells," Adv. Mater., 23(36), 4199-4204 (2011).
[49] C. L. Chen, T. W. Chang, H. Teng, C. G. Wu, C. Y. Chen, Y. M. Yang, and Y. L. Lee, "Highly efficient gel-state dye-sensitized solar cells prepared using poly(acrylonitrile-co-vinyl acetate) based polymer electrolytes," Phys. Chem. Chem. Phys., 15, 3640-3645 (2013).
[50] R. X. Dong, S. Y. Shen, H. W. Chen, C. C. Wang, P. T. Shih, C. T. Liu, J. J. Lin, and K. C. Ho, "A novel polymer gel electrolyte for highly efficient dye-sensitized solar cells," J. Mater. Chem. A, 1, 8471-8478 (2013).
[51] C. Wang, L. Wang, Y. Shi, H. Zhang, and T. Ma, "Printable electrolytes for highly efficient quasi-solid-state dye-sensitized solar cells," Electrochim. Acta, 91, 302-306 (2013).
[52] S. J. Seo, H. J. Cha, Y. S. Kang, and M. S. Kang, "Printable ternary component polymer-gel electrolytes for long-term stable dye-sensitized solar cells," Electrochim. Acta, 145, 217-223 (2014).
[53] T. C. Wei, H. H. Chen, Y. H. Chang, and S. P. Feng, "Hydrophobic electrolyte pastes for highly durable dye-sensitized solar cells," J. Electrochem. Soc., 161(4), H214-H219 (2014).
[54] S. Venkatesan, S. C. Su, W. N. Hung, I. P. Liu, H. Teng, and Y. L. Lee, "Printable electrolytes based on polyacrylonitrile and gamma-butyrolactone for dye-sensitized solar cell application," J. Power Sources, 298, 385-390 (2015).
[55] I. P. Liu, W. N. Hung, H. Teng, S. Venkatesan, J. C. Lin, and Y. L. Lee, "High-performance printable electrolytes for dye-sensitized solar cells," J. Mater. Chem. A, 5, 9190-9197 (2017).
[56] S. Venkatesan, I. P. Liu, J. C. Lin, M. H. Tsai, H. Teng, and Y. L. Lee, "Highly efficient quasi-solid-state dye-sensitized solar cells using polyethylene oxide (PEO) and poly(methyl methacrylate) (PMMA)-based printable electrolytes," J. Mater. Chem. A, 6, 10085-10094 (2018).
[57] M. S. Kang, K. S. Ahn, and J.W. Lee, "Quasi-solid-state dye-sensitized solar cells employing ternary component polymer-gel electrolytes," J. Power Sources, 180, 896-901 (2008).
[58] X. Zhang, H. Yang, H. M. Xiong, F. Y. Li, and Y. Y. Xia, "A quasi-solid-state dye-sensitized solar cell based on the stable polymer-grafted nanoparticle composite electrolyte," J. Power Sources, 160, 1451-1455 (2006).
[59] S. Venkatesan, and Y. L. Lee, "Nanofillers in the electrolytes of dye-sensitized solar cells – A short review," Coord. Chem. Rev., 353, 58-112 (2017).
[60] I. P. Liu, L. W. Wang, M. H. Tsai, Y. Y. Chen, H. Teng, and Y. L Lee, "A new mechanism for interpreting the effect of TiO2 nanofillers in quasi-solid-state dye-sensitized solar cells," J. Power Sources, 433, 226693 (2019).
[61] S. Iijima, "Helical microtubules of graphitic carbon," Nature, 354, 56-58 (1991).
[62] M. N. Lu, C. S. Dai, S. Y. Tai, T. W. Lin, and J. Y. Lin, "Hierarchical nickel sulfide/carbon nanotube nanocomposite as a catalytic material toward triiodine reduction in dye-sensitized solar cells," J. Power Sources, 270, 499-505 (2014).
[63] A. M. Bakhshayesh, M. R. Mohammadi, N. Masihi, and M. H. Akhlaghi, "Improved electron transportation of dye-sensitized solar cells using uniform mixed CNTs–TiO2 photoanode prepared by a new polymeric gel process," J. Nanopart. Res., 15, 1961 (2013).
[64] J. E. Benedetti, A. A. Corrêa, M. Carmello, L. C. P. Almeida, A. S. Goncalves, and A. F. Nogueira," Cross-linked gel polymer electrolyte containing multi-wall carbon nanotubes for application in dye-sensitized solar cells," J. Power Sources, 208, 263-270 (2012).
[65] H. Arakawa et al., "Efficient dye-sensitized solar cell sub-modules,"Curr. Appl. Phys., 10(2), S157-S160 (2010).
[66] Y. Liu, H. Wang, H. Shen, and W. Chen, "The 3-dimensional dye-sensitized solar cell and module based on all titanium substrates," Appl. Energy, 87, 436-441 (2010).
[67] W. J. Lee, E. Ramasamy, and D. Y. Lee, "Effct of electrode geometry on the photovoltaic performance of dye-sensitized solar cells," Sol. Energy Mater. Sol. Cells, 93, 1448-1451 (2009).
[68] Y. D. Zhang, X. M. Huang, K. Y. Gao, Y. Y. Yang, Y. H. Luo, D. M. Li, and Q. B. Meng, "How to design dye-sensitized solar cell modules," Sol. Energy Mater. Sol. Cells, 95, 2564-2569 (2011).
[69] T. C. Wei, Y. H. Chang, S. P. Feng, and H. H. Chen, "A semi-experimental method for fast evaluation of the performance of grid-type dye-sensitized solar module," Int. J. Electrochem. Sci., 8, 9256-9263 (2013).
[70] X. Huang, Y. Zhang, H. Sun, D. Li, Y. Luo, and Q. Meng, "A new figure of merit for qualifying the fluorine-doped tin oxide glass used in dye-sensitized solar cells," Renew. Sust. Energ. Rev., 1, 063107 (2009).
[71] R. Sastrawan, J. Beier, U. Belledin, S. Hemming, A. Hinsch, R. Kern, C. Vetter, F. M. Petrat, A. Prodi-Schwab, P. Lechner, and W. Hoffmann, "New interdigital design for large area dye solar modules using a lead-free glass frit sealing," Prog. Photovolt: Res. Appl., 14, 697-709 (2006).
[72] R. Komiya, A. Fukui, N. Murofushi, N. Koide, R. Yamanaka, and H. Katayama, "Improvement of the conversion efficiency of a monolithic type dye-sensitized solar cell module," in Technical Digest, 21st International Photovoltaic Science and Engineering Conference, pp. 2C-5O (2011).
[73] A. Hauch, and A. Georg, "Diffusion in the electrolyte and charge-transfer reaction at the platinum electrode in dye-sensitized solar cells," Electrochim. Acta, 46, 3457-3466 (2001).
[74] W. Kubo, K. Murakoshi, T. Kitamura, S. Yoshida, M. Haruki, K. Hanabusa, H. Shirai, Y. Wada, and S. Yanagida, " Quasi-solid-state dye-sensitized TiO2 solar cells: effective charge transport in mesoporous space filled with gel electrolytes containing iodide and iodine, " J. Phys. Chem. B, 105, 12809-12815 (2001).
[75] J. E. Benedetti, A. D. Gonçalves, A. L. B. Formiga, M.-A. De Paoli, X. Li, J. R. Durrant and A. F. Nogueira, "A polymer gel electrolyte composed of a poly(ethylene oxide) copolymer and the influence of its composition on the dynamics and performance of dye-sensitized solar cells, " J. Power Sources, 195, 1246-1255 (2010).
[76] Z. Kebede, and S. E. Lindquist, "Donor–acceptor interaction between non-aqueous solvents and I2 to generate I3-, and its implication in dye sensitized solar cells," Sol. Energy Mater. Sol. Cells, 57, 259–275 (1999).
[77] L. Grigorian, K. A. Williams, S. Fang, G. U. Sumanasekera, A. L. Loper, E. C. Dickey, S. J. Pennycook, and P. C. Eklund, "Reversible Intercalation of Charged Iodine Chains into Carbon Nanotube Ropes," Phys. Rev. Lett., 80(25), 5560-5563 (1998).
[78] X. Fan, E. C. Dickey, P. C. Eklund, K. A. Williams, L. Grigorian, R. Buczko, S. T. Pantelides, and S. J. Pennycook, "Atomic Arrangement of Iodine Atoms inside Single-Walled Carbon Nanotubes," Phys. Rev. Lett., 84, 4621-4624 (2000).